Method of preparing 4,5,6, hexachlorotoluyl chloride

ABSTRACT

4,5,6,A,A,A-HEXACHLOROTOLUYL CHLORIDE IS PREPARED BY HEATING 3,4,5,6,7,7-HEXACHLORO-3,6-MENTHANO-1,2,3,6-TETRAHYDROPHTHALOYL CHLORIDE TO AT LEAST 180*C. THE TOLUYL CHLORIDE SO PRODUCED IS A USEFUL CHEMICAL INTERMEDIATE FOR MAKING DYESTUFFS, HERBICIDES, FLAME RETARDANTS AND FLAME PROOFING AGENTS.

United States Patent "ice f flfgiif 3,579,577 01 METHOD OF PREPARING 4,5,6, HEXACHLORO- TOLUYL CHLORIDE o1 FCOCI A o1- Paul E. Hoch, Youngstown, N.Y., assignor to Hooker CClz Chemical Corporation, Niagara Falls, N.Y. Cl- "0001 C1 COC1 No Drawing. Continuation-impart of abandoned applica- H tion Ser. No. g18,15 I17,2Jl;n 8, 1959. This application 01 01 Oct. 9 1962 er. 0. 3 85 Int 01. 51/58 i:r. iittltfiffif i %.:t";:tthl?%% US. Cl. 260-544 2 Claims 10 tetrahydrophthaloyl chloride Another method for preparing 3,4,5,6,7,7-hexachloro- ABSTRACT OF THE DISCLOSURE 3,6-methanol-l ,2,3,6 tetrahydrophthaloyl chloride, the

starting material of th1s invention, is from the treatment 4,5,6,a,a,u-hexachlorotoluyl chloride 1s prepared by f 34,5,6,7,7 hexachlom 3,6 methano 1,2,36 tetrahy heatmg drophthalic anhydride (also known as chlorendic anhyhydrophthaloyl chloride to at least 180 C. The toluyl dride) with phosphorus pentachloride chloride so produced is auseful chemical intermediate for It is a f th finding f this invention that organic making dyestuifs, herbicides, flame retardants and flameesters f 456,a,aa heXach101-o 3-toluYl id may be Proofing agentsprepared by refluxing said chloride with an organic alcohol until solution results.

This invention relates to a novel benzoyl chloride, The following equations typify this esterification reacnovel derivatives thereof and to novel methods for pretion. paring both such chloride and such derivatives. More @913 particularly this invention relates to the new compounds 4,5,6,oc,0z,o hexachloro 3 toluyl chloride, 2,3,4-trichloro 5 trichloromethylbenzoic acid, and to new de- 03,011 rivatives of same such as the anilide of 4,5,6,oz,oz,ot-hXa- C1 0001 chloro-3-t0luic acid and to novel methods of preparation C1 of these compounds as well as others.

This is a continuation-in-part of my earlier filed ap- 3O iifii gfi gififfgfi gfig}? plication Ser. No. 818,517 filed June 8, 1959, now 0013 abandoned. I C C 1,

Utility for some of these compounds is found in the examples which follow. In addition the compounds may r CIHYOH be used in the preparation of polymers, which are, due 01 Cool 01 00004119 to the high chlorine content, flame retardant in nature. 61 C1 The compounds of the present invention may also be used as fiameproofing agents. They also may be used as gigg f gfggi figf gga chemical intermediates and as herbicidal agents. 40

It is a finding of this invention that hexachlorocyclopentadiene may be reacted with fumaryl chloride to yield Various other reactions and preparatrons andproducts 3,45,6,7,7 hexachloro 3,6 methano 12,3,6 tetrahydro prepared thereby although not set forth in equa tlon form, phthaloyl chloride and that this compound when heated W111 be descnbfed helemafter and also compnse Part to a temperature of between about 180 degrees and 220 of the present. mvennon' degrees centigrade or to 140 degrees centigrade with ferric The eXamPleS.are q forth to further chloride catalyst yields 4,5,6,a,a,a-hexachloro-3-toluyl the teachings of thls mvenuon' chloride. The following equations illustrate the foregoing: EXAMPLE 1 The preparation of 4,5,6,oc,u,ot-hX3ChlOIO-3- 0 5O toluyl chloride 01 v A three-necked, round-bottomed flask was charged with I 1 429 grams of fumaryl chloride and 756 grams of hexa- Cl 01 C C chlorocyclopentadiene. The solution was warmed with stirring to 179 degrees to 185 degrees centigrade for in excess of forty-eight hours. The reaction mixture was subgififl gg 5,32 3%? jected to a diminished pressure distillation. After removal 01 of the unreacted hexachlorocyclopentad1ene and fumaryl \/H chloride, the trans acid chloride reaction product of these 01 CO0 two materials began distilling at 175 to 185 degrees centi I 0012 grade at '1217 millimeters, and having a melting point C1- -COCl of 49-50 degrees.

E Analysis.Calcd for C H O Cl (percent): Cl, 66.6.

1 Found (percent): Cl, 66.8.

3,4, 5 6,7,7 E;exach1 ro-3,6- After about 500 grams of this trans acid chloride prodf f ggfi fi igsg' fg uct or adduct was distilled, a solid began to appear and the last out was all solid, having a boiling point of 195 degrees to 203 centigrade at 12 millimeters pressure. The

solid was recrystallized from hexane and had a melting point of degrees to 106 degrees centigrade (uncorrected). Chlorine anal. for C HOCI Theory 68.8%.

0 Found: 68.7%.

The adduction reaction between hexachlorocyclopentadiene and fumaryl chloride is preferably carried out at a temperature between about 140 and 200 degrees centigrade while the decomposition of this adduct is preferably carried out at a temperature between about 180 degrees and 220 degrees centigrade.

EXAMPLE 2 Alternate preparation of 4,5,6,a,u,a-hexachloro-3- toluyl chloride A mixture of 42 grams of the trans acid chloride and 0.3 gram FeCl were heated with stirring at 140-150 degrees centigrade, considerable gasing occurring. The mixture was heated one-half hour and then poured into 100 cc. hexane. The hexane solution was treated with decolorizing charcoal, filtered and cooled. A crystalline solid separated having a melting point of 105 degrees centigrade and identical in infra-red spectrum to be solid isolated in Example 1 above.

EXAMPLE 3 Alternate preparation of 4,5 ,6,0t,O6,0L-heXaChlOI'O-3- toluyl chloride A mixture of 180 grams (0.5 mole) of phosphorus pentachloride and 140 grams (0.67 mole) of cis-3,4,5,6, 7,7-hexachloro-3,6-methano 1,2,3,6 tetrahydrophthalic acid was heated with stirring. A vigorous reaction began at 120-125 C. and the pot temperature rose to 150 degrees centigrade. The resulting solution was warmed at reflux for 8 hours and at the end of this time the phosphorus oxychloride and excess phosphorus pentachloride were stripped under vacuum. The residue, comprising cis- 3,4,5,6,7,7-hexachloro-3,G-methano 1,2,3,6 tetrahydrophthaloyl chloride was heated with stirring to 208-220 degrees centigrade for 3.5 hours during which period 17 grams of hydrogen chloride was evolved. The main product weighing 133 grams (73%) distilled, B.P. 190-195/ 9.0 mm. Recrystallization of the product from hexane gave 75 grams of the rearrangement product 4,5,6,a,a,u-hexachloro-3-toluyl chloride, having a melting point of 105 degrees centigrade.

Analysis.-Calcd. for C HCl O (percent): CI, 68.67. Found (percent): C1, 68.70.

EXAMPLE 4 The preparation of the methyl ester of 4,5,6,cc,oz,a-

hexachloro-3-toluic acid Five grams of 4,5,6,a,oz,a-hexachloro-3-toluyl chloride were refluxed with 10 cc. of methanol until all of the benzoyl chloride went into solution. Upon cooling, a white, crystalline solid separated (needles) having a melting point of 94 degrees to 95 degrees centigrade. Chlorine analysis calculated for C H Cl O Theory 59.7%. Found: 59.6%.

EXAMPLE 5 The preparation of dyestuif from the product of Example 4 A mixture of equal weights of the ester of Example 4, resorcinol and zinc chloride Was heated to 140 degrees to 150 degrees centigrade. The mixture melted and developed a dark red color. After several minutes the reaction mixture was poured into water. A bright brick red solid was obtained which when dissolved in a solution of water and methanol was useful as a dye, for example, to dye wool pink. Also, when the solid was dissolved in a basic solution, it yielded a strong green fluorescent color.

EXAMPLE 6 The preparation of the anilide of 4,5,6,a,a,a-hexachloro- 3-toluic acid Two to three grams of 4,5,6,a,a,a-hexachloro-3-toluyl chloride dissolved in benzene was added to 1 cc. of aniline. A solid separated after an immediate exothermic reaction.

After washing with dilute acid, the isolated solid was recrystallized from methanol and was found to have a melting point of 211 degrees to 212 degrees centigrade. Chlorine anal. for C l-l Cl ON: Theory 51.0%. Found 51.4%.

EXAMPLE 7 The preparation of the butyl ester of 4,5,6,oc,u,a-hexachloro-3 -toluic acid Three grams of 4,5,6,a,u,a-hexachloro-3-toluyl chloride was warmed with 20 cc. butyl alcohol until solution resulted. The solution was cooled to -20 degrees centigrade and white crystals resulted. The solid was recrystallized from butyl alcohol at a low temperature and was found to have a melting point of 48.8 degrees to 49.5 degrees centigrade. Chlorine anal. for C H 'Cl O Theory 53.4% Found: 53.3%

EXAMPLE 8 The preparation of a dyestufi from the product of Example 1 Three and eight tenths grams of 4,5,6,0t,0t,ot-h6X8.ChlOI'O- 3-toluyl chloride, 2.4 grams of dimethyl aniline and 1.3 grams of zinc chloride were heated, with stirring to degrees centigrade. A reaction occurred which was exothermic. After several minutes the reaction product was poured into water. A red-brown solid resulted, which develops a blue color in solvents. When dissolved in a methanol-water solution, it dyes wool a light blue shade.

EXAMPLE 9 Preparation of 4,5 ,6,0t,0t,0L-h6XaCh10lO-3-tOlUlC acid Thirty grams of 4,5,6,oc,a,ot-hexachloro-3-toluyl chloride and 225 grams of formic acid were stirred and heated to 90-100 degrees centigrade for six hours. The final suspension resulting was poured into water. The white solid recrystallized from carbon tetrachloride to yield 19.2 grams, crystals M.P. -194 degrees centigrade, with decomposition.

Analysis.Calcd for C Cl O H (percent): Cl, 62.2 Neutral equiv. 343. Found (percent): Cl, 62.5; Neutral equiv. 342.

Plots infested with a variety of weed species were sprayed with an aqueous dispersion of 4,5,6,ot,oc,zx-h6X3.- chloro-3-toluyl chloride at the rate of 16 pounds per acre prior to the emergence of the weeds, and 8 pounds per acre after emergence of the weeds (separate plots). The results observed about three weeks after spraying are given in the following table:

NOTE.--0=1'1O efiect; 1=slight injury; 2=moderate injury; 3=sevcre injury; 4= complete kill.

An untreated control plot contained a vigorous stand of all the above named weed species.

The acid, organic esters and amide compounds of this invention are also herbicidally active.

Although this invention has been illustrated by citing specific details of given species embraced within the scope of the invention, it is to be understood that various modifications within the invention are possible, some of which have been referred to above; therefore, I do not wish to be limited except as defined by the appended claims.

I claim:

1. A process for preparing 4,5,6,u,a,a-hexachlorotoluyl chloride which comprises heating the compound 3,4,5,6.

5 7,7-hexachloro-3,G-methano-1,2,3,6 tetrahydrophthaloyl chloride of the formula:

n 01 Cl H 8 or in the presence of a catalytic amount of ferric chloride to a temperature of from 140 degrees to 160 degrees centigrade, whereby the toluyl chloride is formed from the rearrangement of said compound.

References Cited UNITED STATES PATENTS 12/1961 Newcomer et a1 260515 5/1964 Weil et a1. 260-476 5/ 1966 Newcomer et al. 71-2.3

11/1957 Newcomer et a] 260468 7/1960 Molotsky 260--5 15 FOREIGN PATENTS 8/1937 France 260-544 CHARLES B. PARKER, Primary Examiner E. J. GLEIMAN, Assistant Examiner US. Cl. XJR.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,579,577 Dated May 18, 1971 Paul E. Hoch Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 52, that portion of the formula reading +-Cl-CCH should read +Cl-C-C-H lines 68 thru 72, cancel the portion of the formula.

Signed and sealed this 25th day of April 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents Column 3, line 18, "to be solid" should read to the solid FORM po'wso uscoMM-oc 6OS7B-PB9 a lLS GOVEHNMINT PRINTING OFFICE I '9. O-Jl-ll 

